Nitroalkyl hexahydroazepines useful as insecticides

ABSTRACT

Novel compounds having the formula WHEREIN R1 and R2 are H or alkyl radicals of one to five carbon atoms, with the proviso that the total number of carbon atoms in R1 plus R2 ranges from one to five. Said compounds are useful as insecticides.

United States Patent Tetenbaum [4 1 Aug. 1, 1972 [54] NITROALKYLHEXAHYDROAZEPINES USEFUL AS INSECTICIDES [72] Inventor: Marvin T.Tetenbaum, Convent,

[73] Assignee: Allied Chemical Corporation, New

York, NY.

[22] Filed: July 28, 1970 [21] Appl. No.: 59,785

[52] U.S. Cl ..260/239 BE, 424/244 [51] Int. Cl. ..C07d 41/08 [58] Fieldof Search ..260/239 BE, 2 H

I [56] References Cited FOREIGN PATENTS OR APPLICATIONS 863,056 1/1953Germany ..260/239 Primary Examiner-Alton D. Rollins Attorney-Arthur J.Plantamura and Herbert G. Burkard [57] ABSTRACT Novel compounds havingthe formula number of carbon atoms in R plus R ranges from one to five.Said compounds are useful as insecticides.

3 Claims, N0 Drawings NITROALKYL I-IEXAHYDROAZEPINES USEFUL ASINSECTICIDES SUMMARY OF THE INVENTION This invention relates to novelnitroalkyl hexahydroazepines and to their use as insecticides.

The novel compounds of this invention have the formula wherein R and Rare H or alkyl radicals of one to five carbon atoms, with the provisothat the total number of carbon atoms in R plus R ranges from one tofive, preferably one to three. Thus R and R cannot both be H.

The compound of the formula N CHaC s ags...

The above hexahydroazepine compounds are solids which are soluble inmany organic solvents such as chloroform and alcohols, but areessentially insoluble in water.

DETAILED DESCRIPTION The synthesis of the compounds of the presentinvention may be carried out by reacting caprolactim-O- methyl etherwith a suitable nitroalkane under reflux conditions. The reactionproduct is stripped of unreacted reagents and the residue thenrecrystallized, preferably from a chloroform hexane mixture. Thereaction may be illustrated by the following general equation:

wherein R, and R are as defined above.

Caprolactim-O-methylether is commercially available or can be preparedby the method described by Benson and Cairns in the Journal of theAmerican Chemical Society, Vol. 70, page 2115 (1948). Essentially themethod involves reacting caprolactam and dimethyl sulfate in benzene.

The compounds of this invention are useful for combatting a wide varietyof insect pests. It will be understood that the term insects as utilizedherein includes not only those small invertebrate animals belongingmostly to the class Insecta, comprising sixlegged, usually winged formssuch as flies, moths, beetles, bees, and their immature forms, but alsoincludes other allied classes of arthropods whose members are Winglessand usually have more than six legs such as mites, spiders andcentipedes.

In using the compounds of this invention as insecticides, the instantcompounds can be used alone or as the active ingredient in aninsecticidal composition which comprises said compounds and diluents,such as in dusts or aqueous sprays.

Since activity of the insecticidal composition increases withconcentration of the active ingredient (i.e., the compound of theinstant invention), the composition may contain 10, 50, or an evenhigher weight percent of the active ingredient. However, for reasons ofsafety and ease of handling, it is preferred that the concentration ofthe active ingredient be limited as outlined in the followingparagraphs.

When employed in the form of a powder or dust, the novel compounds ofthe instant invention may be mixed with a substantial portion of anysuitable inert material or diluent, preferably in finely divided form,such as sulfur, lime, talc, whiting, diatomaceous earth, and knowngrades of prepared insecticide carrier clays including pyrophyllite,fullers earth, and bentonite. Suitable dusts of this type usuallycontain not less than 0.2 percent and preferably from about 2 to about10 percent by weight of active ingredient.

Liquid insecticide sprays containing the active ingredient of thisinvention may be prepared by first forming a solution of the compound ina suitable organic solvent, e.g., chloroform, ethanol, etc., andpreferably adding a small amount of an emulsifying agent of the typecommonly employed in the art such as diglycol oleate, p-isooctyl phenylether of polyethylene glycol, sodium decylbenzene sulfonate and sodiumdodecylbenzene sulfonate. The resulting concentrated solution, usuallycontaining about 2 to 8 pounds of the toxicant per gallon, isincorporated with water in a quantity sufficient to form an aqueousdispersion or emulsion having the desired active ingredientconcentration, as hereinafter described.

In another embodiment, aqueous spray dispersions may be formed byincorporating in water dry mixtures of so-called wettable spray powderscontaining the compounds of the instant invention, generally in anamount of about 15 to 25 weight percent based on the weight of thepowder. These mixtures may also include inert diluents, suitablequantities of wetting and dispersing agents and, if desired, secondarytoxicants.

The above described aqueous spray dispersions preferably contain theactive ingredient in an amount not less than one-fourth of an ounce pergallons of water, the more usual concentration being in the range of 2ounces to 2 pounds per 100 gallons of water.

The novel compounds of this invention are used to combat insects bycontacting said insects with toxic amounts of said compounds eitherdirectly as by depositing the compounds on the insect, or indirectly asby contacting their habitats, e.g., plants, so that the insects willcome in contact with said compounds, e.g., by walking in or brushingagainst said compounds.

The following examples are provided to more fully illustrate the instantinvention. They are provided for illustrative purposes only and are notto be construed as limiting the instant invention, which is defined bythe appended claims.

EXAMPLE 1 A mixture of 12.8 parts by weight caprolactim-O- methyl etherand 19.1 parts by weight l-nitropropane is refluxed overnight. Thereaction mixture obtained is stripped of unreacted reagents undervacuum, leaving 14.0 parts by weight of residue. The residue isrecrystallized from chloroform] hexane giving a 69 percent yield of2-[ethyl nitromethyl]-2,3,4,5,6,7-hexahydroazepine-Al having a meltingpoint of 81-82 C and an analysis as follows:

wt calculated for C H N O C=58.7, H=8.7,

wt found by analysis: C=58.65, H=8.64,

EXAMPLE 2 The procedure of Example 1 is repeated using as reactants 1mole of caprolactim-O-methyl ether and 2 moles each of the followingnitroalkanes: nitroethane, Z-nitropropane, l-nitrobutane,2-nitro-3-methylbutane, and l-nitrohexane. The resultant products are,respectively EXAMPLE 3 Plants containing Mexican bean beetle larvae aretreated with an aqueous spray containing various con- 5 centrations of2-[ethyl nitromethyl]-2,3,4,5,6,7-hexahydroazepine-Al. The percent killafter 3 days is recorded below:

%Kill 80 I00 80 Concentration 2 lb/ 100 gal. H,0 l lb/IOO gal. H 0 802/100 gal. H 0

The products of Example 2 may also be used in a manner similar to theabove compound.

EXAMPLE 4 The products of Example 2 are used to combat a variety ofinsects either by contacting their habitat or by contacting the insectsdirectly in a manner similar to that of Example 3.

We claim:

1. A compound having the formula

2. The compound of claim 1 wherein the number of carbon atoms in R1 plusR2 ranges from one to three.
 3. The compound of claim 1 which is